Reactive additive manufacturing

ABSTRACT

An additive manufacturing method may involve: Providing a first and a second material, the second material capable of reacting with the first material to form a reaction product; forming at least the first material into a first layer; subjecting at least a portion of the first layer to energy in the presence of the second material, the energy being sufficient to initiate a reaction between at least the first and second materials to form a portion of the article, the portion of the article comprising the reaction product; forming a second layer of at least the first material on the first layer; and subjecting at least a portion of the second layer to energy in the presence of the second material, the energy being sufficient to initiate a reaction between the first and second materials to form an additional portion of the article.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of co-pending U.S. patent applicationSer. No. 15/070/514, filed on Mar. 15, 2016, now allowed, which claimsthe benefit of U.S. Provisional Patent Application No. 62/134,190, filedon Mar. 17, 2015, both of which are hereby incorporated herein byreference for all that they disclose.

TECHNICAL FIELD

The present invention relates to additive manufacturing general and moreparticularly to methods and systems for performing additivemanufacturing with reactive materials.

BACKGROUND

Additive manufacturing techniques have been known for decades and arecurrently used to produce a wide range of parts and articles suitablefor any of a wide range of applications. The most, common additivemanufacturing processes may be grouped into three main categories:Powder bed sintering/melting, extrusion, and directed energy depositionby jetting/wire feed. One type of powder bed sintering/meltingtechnique, which may be referred to as selective laser sintering/meltingor direct metal laser sintering, utilizes a laser beam directed energysource to trace a design in a single layer of a powdered material. Theheat from the laser sinters or melts the traced design into a solidpiece with the thickness of that layer. A suitable material feed systemmay dispense another layer of powder on top of the layer just sintered.The process is then repeated until a three dimensional object is formed.However, the energy required to form each layer of material restrictsthe production speed and increases the cost of the equipment needed toproduce an object, with ceramic materials typically requiring moreenergy than do metals, which in turn require more energy than doplastics.

Another process for forming articles is reaction synthesis. Reactionsynthesis is a chemical process that can be used to form sinteredmaterials much more rapidly than is possible with conventional sinteringprocesses. A typical reaction synthesis process involves the mixingtogether of two or more reactants of dissimilar chemistry, typically inpowder form. A die press may be used to compact the mixed powders,forming a compacted article or powder compact. Alternatively, a mold orcrucible may be used to contain the powder mixture. Heat may then beapplied to initiate a chemical reaction among the constituents. Theprocess is often exothermic and results in the formation of one or morenew phases. For example, the heat from a furnace or a flame can initiatea reaction in a mixture of titanium and carbon powder. The combinationreaction releases heat and forms a sintered ceramic phase of titaniumcarbide. The heat produced by this reaction spreads to the powdersaround it, causing the reaction to propagate through any reactantspresent. Some such processes involve the addition of one or more inertspecies, often referred to as diluents, to control the reaction byabsorbing heat.

Reaction synthesis techniques have been used to produce many types ofmaterials including ceramics, metals, intermetallics, polymers, andcomposites. However, most reaction synthesis techniques requireextensive processing steps including the design and fabrication of a dieor mold and typically can only be used to produce articles of simpleshapes with limited detail, thereby limiting such processes.

SUMMARY OF THE INVENTION

One embodiment of an additive manufacturing method of producing anarticle, may involve: Providing a blended powder comprising a firstpowder material and a second powder material, the first and secondpowder materials capable of chemically reacting with one another uponthe addition of energy to form a reaction product, the first powdermaterial being provided in excess of a stoichiometric amount; formingthe blended powder into a first layer; subjecting at least a portion ofthe first layer to energy sufficient to initiate the chemical reactionbetween the first and second materials to form the reaction product,unreacted amounts of the first material absorbing heat produced by thechemical reaction between the first and second materials, the reactionproduct and unreacted amounts of the first material in the first layerforming at least a portion of the article; providing additionalquantities of the blended powder over the first layer to form a secondlayer; and subjecting at least a portion of the second layer to energysufficient to initiate the chemical reaction between the first andsecond powder materials to form the reaction product, the reactionproduct and unreacted amounts of the first material in the second layeralso forming a portion of the article.

Another embodiment of an additive manufacturing method of producing anarticle may involve: Providing a powder comprising a first, material anda metal powder, the first material and metal powder capable ofchemically reacting with one another with the addition of energy to forma reaction product, the metal powder being provided in excess of astoichiometric amount; forming the powder into a first layer; subjectinga portion of the first layer to directed energy sufficient to initiatethe chemical reaction between the first material and the metal to formthe reaction product, unreacted amounts of the metal absorbing heatproduced by the chemical reaction between the first material and themetal, the reaction product nucleating crystallization of the unreactedamounts of the metal to form a crystallized matrix, the reaction productand crystallized matrix forming a portion of the article; providingadditional quantities of the powder over the first layer to form asecond layer; and subjecting at least a portion of the second layer todirected energy sufficient to initiate the chemical reaction between thefirst material and the metal to form the reaction product, unreactedamounts of the metal reducing an extent of propagation of the chemicalreaction between the first material and the metal, the reaction productnucleating crystallization of the unreacted amounts of the metal to forma crystallized matrix, the reaction product and crystallized matrix inthe second layer also forming a portion of the article.

BRIEF DESCRIPTION OF THE DRAWINGS

Illustrative and presently preferred exemplary embodiments of theinvention are shown in the drawings in which:

FIG. 1 is a process flow diagram of a reactive additive manufacturingprocess according to a first embodiment of the present invention;

FIG. 2 is a process flow diagram of a reactive additive manufacturingprocess according to a second embodiment the present invention;

FIG. 3 is a process flow diagram of a third embodiment of a reactiveadditive manufacturing process; and

FIG. 4 is a scanning electron micrograph at 5000× magnification of aportion of an Example 1 article.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

One embodiment of a reactive additive manufacturing process 10 isillustrated in FIG. 1 and may involve providing at least a supply of afirst material 12 and a second material 14. The first and secondmaterials 12 and 14 are capable of reacting with one another upon theaddition of energy to form a final article or product 16. In someembodiments, the first and second materials 12 and 14 may comprisepowders, although the provision of the first and second materials 12 and14 in powder form is not required. For example, in other embodiments,the second material 14 may be provided in gaseous form e.g., in anatmosphere surrounding the first material 12, and made available toreact with the first material 12 at an appropriate time during theprocess. Further, and as will be explained in much greater detailherein, additional materials, such as additional reactant materials 18,diluents 20, liquids 22, and binders 24 may be added, depending on awide range of factors, including the type of final product 16 to beproduced.

In some embodiments, the particular materials being used may be combinedor mixed together, e.g., in a mixer or blender 26, to form a blendedmaterial 28. Blended material 28 may then be formed, e.g., in step 30,into a first layer 32 on a suitable base 34. Alternatively, if only oneprimary constituent is involved (e.g., in embodiments where the secondmaterial 14 is to be provided in gaseous form), the blending step may beomitted and the first layer 32 may be formed solely from the firstmaterial 12. In some embodiments, the first layer 32 may be formed bycompacting the materials (e.g., either first material 12 or blendedmaterial 28) in an optional compaction process 36. Alternatively and/oradditionally, the various materials (e.g., first material 12 or blendedmaterial 28) may be subjected to an optional evaporation process 38 toremove any liquid components that may be present in either the firstmaterial 12 or the blended material 28, as the case may be.

Regardless of the particular materials and processes that may be used toform first layer 32, reactive additive manufacturing process 10 may thenadvance to step 40 in which at least a portion of the first layer 32 issubjected to energy sufficient to initiate a reaction between at leastthe first and second materials 12 and 14, thereby forming a reactionproduct. In some embodiments, the energy may be provided by a beam ofdirected energy 42, such as a laser beam 44. In other embodiments, theenergy may be provided by a localized energy source, such as a heater orhot filament 243 (FIG. 3). In an embodiment wherein the energy isprovided by a directed energy beam 42, the beam of directed energy 42may be caused to move over the first layer 32 in the desired pattern,the result will be the formation of a reacted portion or layer 32′ ofthe article 16 being manufactured. The reacted portion or layer 32′ ofarticle 16 will comprise primarily the reacted product, although it mayalso comprise other materials in lesser amounts, such as unreactedamounts of the first and second materials 12 and 14 and/or partiallyreacted products of the first and second materials 12 and 14. Dependingon the particular embodiment, step 40 may be conducted in the presenceof a process gas 46, such as a reactive gas (e.g., which may comprisethe second material 14 in some embodiments) or an inert gas.Alternatively, step 40 may be conducted in a vacuum 48 or a partialvacuum.

After the first layer 32 of the desired article 16 has been reacted toform reacted first layer 32′, step 30 may be repeated in which a secondlayer 50 is formed over the just-reacted first layer 30′. Thereafter,step 40 may again be performed in which energy (e.g., from directedenergy beam 42) is provided to the second layer 50 in an amountsufficient to initiate a reaction between at least the first and secondmaterials 12 and 14 in order to form a reacted second layer 50′ of thearticle 16. The reacted second portion or layer 50′ of article 16 againwill comprise primarily the reaction product of at least first andsecond materials 12 and 14, although it may comprise other materials aswell. After it is determined that the article 16 is complete, e.g., atstep 52, the process 10 may be terminated.

Depending on the particular embodiment, the as-produced article 16 maybe surrounded by unreacted portions of the first and second materials 12and 14 used to form the various reacted layers, e.g., 32′ and 50′. Suchmaterial may be removed, e.g., mechanically, to reveal the final productor article 16.

A significant advantage of the present invention is that it may be usedto produce articles comprising a wide range of shapes, materialcompositions, and mechanical or structural properties. In particular,existing additive manufacturing methods for producing high strengthparts typically use homogeneous powder materials of the same compositionas the desired product composition. This approach has resulted in alimited selection of materials that can be successfully utilized byexisting additive manufacturing processes to produce high quality parts.The existing materials selection for the most common commerciallyavailable additive manufacturing processes is currently limitedprimarily to polymers and specific metal alloys. Since most existingadditive manufacturing processes rely on heating layers of a part tonear or above the melting temperature of the material, high temperaturematerials like many ceramics require high energy input and are difficultto manufacture with these processes. Due to the limitations of existingprocesses, ceramics, intermetallics, and metal ceramic compositematerials are largely unavailable for use with additive manufacturingprocesses.

In the case of ceramic materials, the properties of ceramic articlesproduced by conventional ceramic processing techniques can often beimproved by use of ceramic constituent powders with small particle sizes(e.g. less than about 10 μm and often less than about 1 μm diameter) toproduce fine grained sintered ceramic articles. Such extremely fineparticle sizes cannot be used in most existing powder bed additivemanufacturing processes because the poor flowability of the fine powdersresults in difficulty obtaining an evenly spread layer.

In contrast to the various limitations, drawbacks, and disadvantagesassociated with known fabrication processes, the reactive additivemanufacturing processes of the present invention provides forsignificant improvements and options in terms of material composition,energy requirements, and ease of manufacture.

For example, in embodiments where energy is released by an exothermicchemical reaction between the various constituents (e.g., first andsecond materials 12 and 14), less external energy input is required toachieve fusion of the powder form materials into a complete article 16.The lower external energy requirement allows for increased manufacturingspeeds and/or reduced equipment costs. The invention allows additivemanufacturing techniques to use materials that were not consideredpossible or practical with conventional additive manufacturingprocesses. Since the melting points of the reactant materials are oftenbelow the melting points of the product materials, the in-situ productsynthesis utilized by the present invention can result in improvedproduct densities compared to conventional additive manufacturingtechniques that attempt to directly sinter or melt the high temperatureproduct phase. In addition, since the product phases are formed in-situ,fine grained product materials can be formed even with use of relativelylarge-sized reactant materials. This allows for improved productproperties while maintaining optimal powder flow and spreadingcharacteristics for the blended mixture.

The use of constituent reactant materials also allows for increasedflexibility to easily modify mixture compositions by changing the ratiosof the constituent materials. For example, a blended mixture designed toproduce a ceramic-metal matrix composite with 20 vol. % ceramic couldeasily be modified to instead produce a 25 vol. % ceramic-metal matrixcomposite. This flexibility is particularly useful for development workbut can also be useful for readily customizing the material propertiesbased on the specific combination most suitable for the product article.

Having briefly described one embodiment 10 of the reactive additivemanufacturing process according to the present invention, as well assome of its more significant features and advantages, variousembodiments, modifications, and alternative arrangements possible withthe present invention will now be described in detail. However, beforeproceeding with the detailed description, it should be noted that thevarious exemplary embodiments are shown and described herein as theycould be used with certain starting materials to make articlescomprising reactive components of those materials. However, and as wouldbecome apparent to persons having ordinary skill in the art after havingbecome familiar with the teachings provided herein, the presentinvention may be used with a wide variety of starting materials to forma wide variety of articles comprising a wide range of shapes,compositions, material, and structural properties. Accordingly, thepresent invention should not be regarded as limited to the particularmaterials, process steps, article shapes, compositions, and materialproperties shown and described herein.

Referring back now to FIG. 1, a reactive additive manufacturing process10 according to one embodiment of the present invention may compriseproviding a supply of a first material 12 and a second material 14. Atleast the first and second materials 12 and 14 are capable of reactingwith one another upon the addition of energy to form a reaction productor products. As mentioned earlier, optional reactant materials 18 may beadded that may react with materials 12 and 14 to form the reactionproduct or products.

In some embodiments, one or more diluent materials 20 may be added toabsorb heat and reduce the reaction rate, reaction temperature, and thepropagation rate and/or extent of the reaction. The additional diluentmaterials 20 may participate in the reaction as intermediary reactants,solvents, or catalysts that may reduce the energy input required toinitiate the primary chemical reactions (e.g., between first and secondmaterials 12 and 14 and any additional reactant materials 18). When oneor more diluent materials 20 are added, it may be desirable to usepre-synthesized product materials of the same composition as one or moreof the reaction products. It also may be desirable to use diluentmaterials 20 that confer beneficial properties to the article 16, suchas metals or alloys, to serve as a matrix for reaction synthesizedceramic phases. Diluent materials 20 may also be chosen to provide otheradvantages such as aid in sintering of the product phases or to inhibitgrain growth.

Reaction equations may be used to determine stoichiometric ratios forthe relative quantities of the participating reactant species. Thestoichiometric ratios can be readily converted to mass ratios using themolecular/atomic weights of the species, as would become apparent topersons having ordinary skill in the art after having become familiarwith the teachings provided herein. The chemical energy released orabsorbed by the reaction can be calculated with the use of tabulatedchemical thermodynamic data tables such as the JANAF ThermochemicalTables, which are specifically incorporated herein by reference for allthat they disclose. The calculated reaction energy can be used withtemperature-dependent heat capacity and phase change energy data tocalculate the adiabatic reaction temperature for the desired materialsystem. The energy of the reaction, temperature dependent heat capacitydata, and the energy density input from the directed energy beam 42 orlocalized energy (e.g., from heater or filament 243, FIG. 3) can be usedto estimate the adiabatic peak temperatures that may be obtained duringprocessing step 40.

For exothermic chemical reactions, the heat input by the directed energysource or localized energy source and the heat released by the chemicalreaction will be conducted by the material to adjacent regions and maybe sufficient to initiate the chemical reaction in these adjacentregions. In cases where the heat released by the chemical reaction aloneis adequate to initiate the reaction in adjacent layers, the reactionmay propagate throughout the contacting reactant material. In caseswhere the heat released by the chemical reaction alone is not adequateto initiate the reaction in adjacent layers, limited local reactionpropagation may still occur due to the additional heat input from thedirected energy source 42 or localized energy source 243. The distanceof the local reaction propagation is affected by the energy input fromthe directed energy source and the energy released by the chemicalreaction. As already mentioned, one or more diluent materials 20 may beutilized to control the extent and/or rate of propagation.

For powder bed embodiments (e.g., wherein the various layers 32, 50 areformed from powders), limited localized reaction propagation may bebeneficial by allowing for increased processing speed and a favorablemicrostructure, however excessive propagation is generally not desirablebecause it will reduce the detail and tolerances that can be achieved bythe additive manufacturing process. Therefore, for powder bedembodiments, it is generally preferable to design the reactant systemsto limit reaction propagation.

Further, in embodiments wherein the materials are provided in powderform, it may be generally desirable to use powders having sphericalshapes or morphologies due to their flowability. That is, the use offlowable powders improves the ability to distribute the powder intouniform layers. Powder flowability is also affected by the diameters ofthe particles, with particles that are too small having poor flowcharacteristics and particles that are too large limiting the ability toproduce fine article detail and hindering chemical activity.

The particle sizes of each of the constituent powders may individuallybe controlled by the powder manufacturing techniques or classificationsteps (e.g. sieving) to provide powders of the desired sizes. Thepreferred size of each constituent powder may be based on theconstituent material properties including density, morphology,hygroscopicity, oxygen affinity and oxide/hydroxide layercharacteristics, and electrostatic interactions, again as would becomeapparent to persons having ordinary skill in the art after having becomefamiliar with the teachings provided herein.

Referring back now to FIG. 1, it may also be desirable to add one ormore liquids 22 and/or binders 24 to the mixture. Liquids 22 and/orbinders 24 may be added to improve the flowability of the fine particles(e.g., materials 12, 14, 18, and 20) by binding them into agglomeratesor to form a paste, slurry, suspension, colloidal suspension, orplastically deformable composite material. Any added liquids 22 and/orbinders 24 may be selected to volatilize or decompose following thelayer formation prior to or during the application of energy to initiatethe chemical reaction. Such materials 22 and 24 also may participate inthe chemical reaction to form product phases in the article 16.

By way of example, liquid 22 and/or binder 24 may comprise any of a widerange of waxes, polymers, or other low-melting temperature material thatis a liquid, viscous liquid, or capable of undergoing viscous flow atroom temperature or otherwise prior to or during the blending step.

The first and second materials 12, 14, and optionally any reactant,diluent, liquid, and/or binder material(s) 18, 20, 22, and 24 may becombined or mixed together in a suitable mixer 26 to form blendedmaterial 28. Mixer 26 may comprise any of a wide range of mixingdevices, such as tumblers, mixers, ball mills, or blenders, that, areknown in the art or that may be developed in the future that are (orwould be) suitable for the particular application (e.g., the formationof a slurry or colloidal suspension) and materials involved. Theresulting blended material 28 may be spread to form first layer 32 instep 30. The blended material 28 may be so formed by any of a wide rangeof spreading and forming devices (not shown), such as, for example,coating blades, brushes, rollers, sprayers, or dispensers that are nowknown in the art or that may be developed in the future that are (orwould be) suitable for forming the desired layers.

The first layer 32 may be spread or formed on a suitable base plate 34.Alternatively, the first layer 32 may be formed on a pre-existingarticle 34′ which may comprise the same materials as the article 16. Insuch an embodiment, the article 16 so formed may be welded or otherwisebonded to the pre-existing article 34′, although this is not required.

The material (e.g., the first material 12 alone, or the blended material28) forming the various layers (e.g., 32, 50) optionally may becompressed or compacted, e.g., at step 36, to form a compacted layer.Such a compaction step may be accomplished by any of a wide range ofcompaction devices, such as press plates, dies, or rollers.Alternatively, the various layers (e.g., 32, 50), may be compacted orcompressed by means of isostatic pressure. If a liquid 22 and/or binder24 was added, then the liquid 22 and/or binder material 24 may foeevaporated or decomposed in step 38. Step 38 may involve the applicationof heat and/or reduced pressure (e.g., a vacuum or partial vacuum) for atime sufficient to evaporate or decompose the liquid 22 and/or binder24.

Thereafter, at least a portion of the layer 32 may then be subjected toenergy (i.e., during step 40) sufficient to initiate the reactionbetween at least some of the materials comprising the layer 32. In someembodiments, energy sufficient for initiating the reaction may beprovided by a directed energy beam 42 that may be caused to be directedover the layer 32 in the desired pattern. Directed energy beam 42 maycomprise any of a wide range of directed energy beams, such as a laser(or similar type of electromagnetic radiation) beam 44, an electron (orother particle) beam, or an electric plasma arc. In other embodiments,the energy required to initiate the reaction may comprise a source oflocalized energy, such as a hot filament or heater 243 (FIG. 3)positioned adjacent the layer 32.

The temperature required to initiate the chemical reaction for aspecific system (i.e., combination of materials in the layer 32) can bedetermined experimentally, obtained from literature, or estimatedtheoretically. The reaction initiation temperature can be converted toan energy requirement using heat capacity and phase change energy datafor the reactant materials, as would become apparent to persons havingordinary skill in the art after having become familiar with theteachings provided herein.

In embodiments utilizing a directed energy beam 42, the directed energybeam 42 may be configured or adapted to provide sufficient energy to theportion of the layer 32 to initiate reactions between materials in theblended mixture 28 thereby forming the reaction products and fusing thematerials together to form a reacted layer 32′ in the article 16. If thefirst layer 32 was spread onto a base plate 34 or pre-fabricated article34′, the directed energy beam 42 and/or reaction energy may also fusethe reacted first layer 32′ to the base plate 34 or article 34′.

As briefly mentioned earlier, and depending on the particularembodiment, step 40 may be conducted in the presence of a process gas46, such as a reactive gas (e.g., which may comprise the second material14 in some embodiments) or an inert gas. Alternatively, step 40 may beconducted in a vacuum or partial vacuum 43. If so, process 40 may beconducted in a suitable process chamber 54.

As mentioned, the reacted portion or layer 32′ of article 16 maycomprise primarily the equilibrium phases including the reactantproducts and optional diluent materials, although it may also comprisein lesser amounts non-equilibrium phases including unreacted reactantmaterials and intermediary compounds of the first and second materials12, 14, and optionally additional reactant materials 18, diluentmaterials 20, and liquid/binder materials 22 and 24.

After the first layer 32′ of the desired article 16 has been fullyformed, step 30 may be repeated in which additional amounts of thereactive material(s) (e.g., first material 12 or blended material 28,depending on the particular embodiment) are spread or formed into asecond layer 50 over the just-formed layer 32′ of the article 16.Thereafter, step 40 may again be performed in which the directed energysource or beam 42 is directed over the second layer 50 in order to forma second reacted portion or layer 50′ of the article 16. The secondportion or reacted layer 50′ of the article 16 again may compriseprimarily the equilibrium product phases, although it may also compriseother non-equilibrium phases as well. The steps of adding additionallayers (in step 30) and subjecting them to directed energy (in step 40)may be repeated until it is determined at step 52 that the article 16 iscomplete. When the article 16 is complete, the process 10 may beterminated.

In many embodiments, the manufactured article 16 will be surrounded byunreacted and non-fused portions of the material used to form thevarious layers. Such materials may be removed (e.g., mechanically), toreveal the final product or article 16.

A second embodiment 110 of the reactive additive manufacturing processis illustrated in FIG. 2 and also may involve providing a supply of afirst material 112 and second material 114. However, in the secondembodiment 110, the second material 114 may be provided in gaseous formto a suitable process chamber 154 so that the gaseous material 114 formsan atmosphere around the various layers 132, 150. Thus, second material114 may be referred to herein in the alternative as a process gas 146.The first material 112 is capable of reacting with the gaseous material114 upon the addition of energy to form a reaction product or products.

Before proceeding with the description it should be noted that in otherembodiments the second material 114 need not be provided in gaseousform. For example, in other embodiments, the second material 114 may beprovided as a vapor, mist, spray or liquid. In still yet otherembodiments, the second material 114 may be provided in wire, tube orstrip form. In such embodiments, the wire, tube, or strip of secondmaterial 114 may be provided in the form of a consumable electrode toprovide directed energy in the form of a plasma arc or electron beam.

As was the case for the first embodiment 10, one or more additionalreactant material(s) 113 may optionally be added that may react withmaterials 112, 114 to form a reaction product or products. One or morediluent material (s) 120 also may be added to absorb heat and reduce thereaction rate, reaction temperature, reaction extent, or amount ofpropagation of the reaction. As already described, the additionaldiluent materials 120 may participate in the reaction as intermediaryreactants, solvents, or catalysts that may reduce the energy inputrequired to initiate the primary chemical reactions. When diluentmaterials 120 are added, it may be desirable to use pre-synthesizedproduct materials of the same composition as one or more of the reactionproducts. It also may be desirable to use diluent materials 120 thatconfer beneficial properties to the final article 116 such as metals oralloys to serve as a matrix for reaction synthesized ceramic phases.Diluent materials 120 may also be chosen to provide other advantagessuch as aid in sintering of the product phases or to inhibit graingrowth.

Here again, and as was the case for the first embodiment 10, reactionequations may be used in the second embodiment 110 to determinestoichiometric ratios for the relative quantities of the participatingreactant species. The stoichiometric ratios can be readily converted tomass ratios using the molecular/atomic weights of the particular speciesinvolved. The chemical energy released or absorbed by the reaction canbe calculated with the use of tabulated chemical thermodynamic datatables such as the JANAF Thermochemical Tables. This calculated reactionenergy can be used with temperature dependent heat capacity and phasechange energy data for all constituents to calculate the adiabaticreaction temperature for the material system. The energy of thereaction, temperature dependent heat capacity data, and the energydensity input from the directed energy source can be used to estimatethe adiabatic peak temperatures that may be obtained during processing.

For exothermic chemical reactions, the heat input by the directed energysource and the heat released by the chemical reaction will be conductedby the material in layer 132 to adjacent regions and may be sufficientto initiate the chemical reaction in these adjacent regions. In caseswhere the heat released by the chemical reaction alone is adequate toinitiate the reaction in adjacent layers (e.g., second layer 150), thereaction may propagate throughout the contacting reactant material. Incases where the heat released by the chemical reaction alone is notadequate to initiate the reaction in adjacent layers, limited localpropagation may still occur due to the additional heat input from thedirected energy source 142. The distance of the local propagation isaffected by the energy input from the directed energy source 142 and theenergy released by the chemical, reaction. Diluent materials 118 may beutilized to control the extent of propagation.

In most variations of the second embodiment 110, the first material 112and optional materials 116 and 118 will comprise powders, although theprovision of powder form is not required. Here again, spherical powdermorphologies are generally preferred to improve the ability todistribute the powder into a uniform layer (i.e. the powderflowability.) The powder flowability is also affected by the diametersof the particles with particles that are too small having poor flowcharacteristics and particles that are too large limiting the ability toproduce fine article detail and hindering chemical activity. Theparticle sizes of each of the constituent powders may individually becontrolled by the powder manufacturing techniques or separationtechniques (e.g. sieving) to provide powders of the desired sizes. Thepreferred size of each constituent powder may be based on theconstituent material properties including density, morphology,hygroscopicity, oxygen affinity and oxide/hydroxide layercharacteristics, and electrostatic interactions.

It may also be desirable in the second embodiment 110 to add one or moreliquids 122 and/or binders 124 to the first material 112. Here again,liquids 122 and/or binders 124 may be added to improve the flowabilityof the first material 112 and/or any added materials (e.g., materials118 and 120) by binding them into agglomerates or to form a paste,slurry, suspension, colloidal suspension, or plastically deformablecomposite material. Any added liquids 122 and/or binders 124 may beselected to volatilize or decompose following the layer formation priorto or during the application of energy to initiate the chemicalreaction. Such materials 122 and 124 also may participate in thechemical reaction to form product phases in the article 116. Liquid 122and/or binder 124 may comprise any of a wide range of waxes, polymers,or other low-melting temperature material that is a liquid, viscousliquid, or capable of undergoing viscous flow at room temperature orotherwise prior to or during the blending step.

The first material 112 and optionally any additional reactant, diluent,liquid, and/or binder material(s) 118, 120, 122, and/or 124 may becombined or mixed together, e.g., in a suitable mixer 126 to form ablended material 128. The resulting blended material 128 may be spreadon a base 134 or pre-existing article 134′ in step 130 to form a firstlayer 132. As was the case for the first embodiment 10, any of a rangeof spreading or forming devices, such as coating blades, brushes,rollers, sprayers, or dispensers, may be used for this purpose.

The material (e.g, the first material 112 alone or the blended material128) forming the various layers optionally may be compressed orcompacted at step 136 to form a compacted layer. Again, any of a widerange of compaction devices, such as press plates, dies, or rollers maybe used for this purpose. The layers may also be compressed or compactedby means of isostatic pressure. If a liquid 122 or binder 124 was added,then such material 122 and 124 may be evaporated or decomposed inoptional evaporation step 138. Step 138 may involve the application ofheat and/or reduced pressure for a time sufficient to evaporate ordecompose substantially all of the liquid and/or binder material 122,124, as the case may be. Here again, the compaction and evaporationsteps 136 and 133 may be conducted separately or in combination.Alternatively, neither the compaction nor evaporation steps 136 and 138need be conducted.

In the second embodiment 110, the second material 114 (i.e., which maycomprise process gas 146) may be introduced into the process chamber154. The process gas 146 may comprise a single reactive gas type (e.g.,second material 114), multiple reactive gas types, or a reactive gastogether with one or more inert gases, e.g. argon.

Thereafter, the first layer 132 may be subjected to energy during step140 to form a reacted portion or layer 132′ of the article 116 to bemanufactured. Here again, the energy provided may comprise directedenergy (e.g., from a directed energy beam 142). Alternatively, theenergy may comprise localized energy, such as from a hot filament orheater 243 (FIG. 3). The process gas 146 (i.e., which may comprisesecond reactant material 114) may be provided at controlled pressures,flow rates, and/or ratios to control the reaction products, rates, peaktemperatures, reaction propagation, or extent of completion during thereaction process. For variations involving process chamber 154, theatmosphere of process gas 146 may be maintained during layer spreadingthrough subjection to energy at step 140, including optional compaction136 and/or evaporation 138 steps. In embodiments wherein the processchamber 154 may also serve as a pressure vessel, the pressure of theprocess gas 146 may be selected to be maintained at any desiredpressure, i.e., above or below ambient pressure. Alternatively, process140 may be conducted in a vacuum or partial vacuum 148.

In embodiments wherein the energy required to initiate the reaction isprovided by directed energy, the directed energy beam 142 may becontrolled or configured to provide sufficient energy to the portion ofthe layer 132 to initiate reactions between the materials, therebyforming the reaction products and fusing the materials together to forma reacted layer 132′. If the first layer 132 was spread onto acompatible base plate 134 or pre-fabricated article 134′, then thedirected energy beam 142 and/or reaction energy may also fuse the firstlayer 132′ to the plate 134 or pre-fabricated article 134′. The reactionproducts may include products formed by reaction of components of thereactive material(s) in blended mixture 128, products formed by reactionof components in the blended mixture 128 with the various species (i.e.,second reactant 114) comprising process gas 146, and products formed byreaction of components of the process gas 146 reacting with othercomponents in the process gas 146. The reacted layer 132′ may alsocomprise equilibrium phases including the reactant products and optionaldiluent materials, although it may also comprise non-equilibrium phasesincluding unreacted reactant materials and intermediary compounds ofcomponents of the blended materials 128 and process gas 146.

After the first layer 132′ of the desired article 116 has been fullyformed, step 130 may be repeated in which additional amounts of theblended material 128 are spread, formed, or (optionally) compacted overthe just-formed layer 132′ of the article 116 to form a second layer150. Thereafter, step 140 again may be performed in which the directedenergy beam 142 is directed over the second layer 150 in order to form asecond reacted portion or layer 150′ of the article 116 to bemanufactured. The second portion or layer 150′ of the article 116 againmay comprise the equilibrium product phases of the various constituents,although it may also comprise other non-equilibrium phases as well. Thesteps 130 and 140 of adding an additional layer and subjecting it todirected energy may be repeated until it is determined at step 152 thatthe article 116 is complete. When the article 116 is complete, theprocess 110 may be terminated. In most versions of this secondembodiment 110, the manufactured article 116 will be surrounded byunreacted and non-fused portions of the blended material 128 used toform the various layers (e.g., 132′, 150′). Such materials may beremoved (e.g., mechanically), to reveal the final product or article116.

Still other variations and modifications of the present invention arepossible. For example, and with reference now primarily to FIG. 3, athird embodiment 210 of a reactive additive manufacturing processaccording to the present invention may involve the formation of ablended paste material 228 which thereafter may be extruded at step 230to form a ‘green’ article 215. Depending on the particular final article216 that is to be produced, green article 215 may comprise substantiallythe entirety of the final article 216. Alternatively, green article 215may comprise a smaller portion, or ever, an individual layer 232 of thefinal article 216.

Once the green article 215 or layer 232 has been fully formed, it maythen be heated e.g., by a heater 243, to initiate one or more chemicalreactions and form the final article 216. Alternatively, the greenarticle 215 or layer 232 may be subjected to a directed energy beam 242prior to adding subsequent layers 250. The heat or directed energy maypartially or fully fuse the layers 230, 250 and may or may not besufficient to initiate one or more chemical reactions in the layers. Inthis embodiment, if the chemical reactions have already formed thedesired product phases when subjecting the layers to heat or directedenergy, the fully formed article 216 may comprise the final article 216without, the requirement for further subjection to heat, e.g., duringstep 256. The most substantial, difference in this third embodiment 210compared to the first embodiment 10 is that the blended material 228 isapplied only to the layer locations where the article is to be formed asopposed to being spread over an entire bed as was the case in the firstembodiment 10.

More specifically, method 210 may involve providing first and secondmaterials 212 and 214 and optionally additional reactant and diluentmaterials 218 and 220. As was the case for the first and secondembodiments 10 and 110, the first and second materials 212 and 214 andoptional reactant materials 218 are capable of reacting with one anotherupon the addition of energy to form a desired reaction product orproducts for the formation of the article 216.

As was the case for the other embodiments 10 and 110, one or morediluents 220 may be added to absorb heat and/or reduce the reactionrate, reaction temperature, and amount of propagation of the reaction.The additional diluent materials 220 may participate in the reaction asintermediary reactants, solvents, or catalysts that may reduce theenergy input required to initiate the primary chemical reactions. Whendiluent materials 220 are added, it may be desirable to usepre-synthesized product materials of the same composition as one or moreof the reaction products. It also may be desirable to use diluentmaterials 220 that confer beneficial properties to the article such asmetals or alloys to serve as a matrix for reaction synthesized ceramicphases. Diluent materials 220 may also be chosen to provide otheradvantages such as aid in sintering of the product phases or to inhibitgrain growth.

In many embodiments, the first and second materials 212 and 214, andoptional additional reactant and diluent materials 218 and 220 may beprovided in powder form, although the provision of these materials inpowder form is not required. Once the first and second materials 212 and214 and optional additional reactant and/or diluent materials 218 and/or220 have been provided, they may be combined or mixed together, e.g., ina suitable mixer 226 to form a blended material 228. In most variationson this embodiment 210, the blended material 226 should comprise a pasteor paste-like material (e.g., a slurry or colloid) suitable for laterextrusion. Accordingly, in the particular embodiment shown and describedherein, a liquid 222 and/or a binder 224 may be added during theblending process to form the blended paste or paste-like material 228.

As was the case for the other embodiments 10 and 110, reaction equationsmay be used in the embodiment 210 to determine stoichiometric ratios forthe relative quantities of the participating reactant species. Thestoichiometric ratios can be readily converted to mass ratios using themolecular/atomic weights of the species. The chemical energy released orabsorbed by the reaction can be calculated with the use of tabulatedchemical thermodynamic data tables such as the JANAF ThermochemicalTables. The calculated reaction energy can be used withtemperature-dependent heat capacity and phase change energy data for allconstituents to calculate the adiabatic reaction temperature for thematerial system. The energy of the reaction, temperature-dependent heatcapacity data, and the energy density input from the directed energysource can be used to estimate the adiabatic peak temperatures that maybe obtained during processing.

For exothermic chemical reactions, the heat input at step 240 (or step256) together with the heat released by the chemical reaction will beconducted by the reacting material to adjacent regions may be sufficientto initiate the chemical reaction in these adjacent regions. In caseswhere the heat released by the chemical reaction is adequate to initiatethe reaction in adjacent layers, the reaction may propagate throughoutthe reactant material. In cases where the heat, released by the chemicalreaction alone is not adequate to initiate the reaction in adjacentlayers, limited local propagation may still occur due to the additionalheat input from the directed energy source 242 or heater 243. Thedistance of the local propagation is affected by the energy input fromthe directed energy source 242 or heater 243 and the energy released bythe chemical reaction. Again, one or more diluent materials 220 may beutilized to control the extent of reaction propagation. For extrusionbased embodiments, such as third embodiment 210, full propagation of thechemical reaction may be desirable.

After the various constituent materials have been combined and blendedtogether, the resulting blended paste material 228 may be extruded instep 230 to form the green article 215 or a portion or layer 232 of thearticle to be manufactured. Any liquid and/or binder materials 222and/or 224 that were added may optionally be evaporated or decomposedfrom the extruded material in step 238 by application of heat and/orreduced pressure for a sufficient time. In step 240, the extruded layer232 may optionally be subjected to directed energy beam 242 or heat froma heater 243 in order to partially or fully fuse the material to form afused or reacted layer 232′. In this embodiment it should be noted thatthe energy provided by directed energy beam 242 or heater 243 duringstep 240 may or may not be sufficient to initiate one or more chemicalreactions in the green article 215 or layer 232. In this variation, ifthe chemical reactions have already formed the desired product phaseswhen subjecting the various layers (e.g., 232, 250) to heat or directedenergy, the fully formed article may be the final article 216 withoutthe requirement for further subjection to heat at step 256.

Depending on the particular materials involved and/or the final article216 to be produced, step 240 may be conducted in the presence of aprocess gas 246. Process gas 246 may comprise a reactive gas or an inertgas. If so, process 240 may be conducted in a suitable process chamber254. Alternatively, step 240 may be conducted in a vacuum or a partialvacuum 248.

Additional extruded layers (e.g., second layer 250) may be added untilthe article is fully formed, e.g., as determined at step 252. In avariation of the third embodiment 210, the extrusion process mayprogress in a continuous manner without discontinuation of the extrusionprocess between layers. In such a continuous extrusion process, theoptional application of heat or directed energy may also progress in acontinuous manner until the article 216 is fully formed. If the articlelayers have not been subjected to heat or directed energy sufficient toinitiate the chemical reactions to form the desired product phases(i.e., during step 240), the formed or manufactured article willcontinue to comprise a ‘green’ article 215, and will comprise theunreacted materials (e.g., first and second materials 212 and 214 andoptionally additional reactant materials 218, diluent materials 220, andany liquid and/or binder materials 222 and/or 224 comprising the blendedpaste 228.

Thereafter, the green article 215 may be heated at step 256 in order toinitiate the reaction between the first and second materials 212 and 214and optional additional reactant materials 218, diluent materials 220,and any liquid and/or binder materials 222, 224. The temperature andtime required to initiate and complete the chemical reaction for aspecific system can be determined experimentally, obtained fromliterature, or estimated theoretically. The reaction initiationtemperature can be converted to an energy requirement using heatcapacity and phase change energy data for the reactant materials.

The result will be a final article 216 comprising primarily the reactionproduct of first and second materials 212 and 214 and optionallyadditional reactant materials 218 and liquid and/or binder materials 222and/or 224, as well as any optional diluent materials 220. Depending onthe particular materials involved, any liquid and/or binder materials222 and/or 224 used to form the blended paste 228 may be removed eitherduring the optional evaporation step 238 or during the heating steps 240or 256. The liquid and/or binder materials 222 and/or 224 mayalternatively decompose instead of fully evaporate or participate in thechemical reactions to contribute to the product phases.

EXAMPLES Reaction Equation Examples

A wide range of product materials can be produced by the methodsdescribed in this invention. The invention can be used to producematerials including metals, intermetallics, ceramics, composites, andpolymers. Examples of suitable reactions are given below to illustratethe versatility of the process and the inventions should not be limitedby these examples. The stoichiometric coefficients (unity where notindicated) represent the number of moles of each species. The variablesx and y are used to represent diluent coefficients that can be varied toadjust the reaction temperature and/or product composition. Thecalculated adiabatic combustion temperature, T_(ad), with a startingtemperature of 298 K is given for the solid phase reactions for theindicated stoichiometric coefficients.

TABLE I Example Reactions Reactants Products Energy (kJ) T_(ad(298K))(K) Ti + C TiC −185 3433 Ti + 2B TiB₂ −280 3450 3Ti + B₄C 2TiB₂ + TiC−682 3230 Si + C SiC −72 1852 W + C WC −40 1164 B + 4C B₄C −62 957 Ni +Ti NiTi −68 1438 Mo + 2Si MoSi₂ −119 1799 4Al + 3TiO₂ + 3C 2Al₂O₃ + 3TiC−1071 2355 Ti + Si + 2C TiC + SiC −256 2763 B₂O₃ + Ti + 2Al TiB₂ + Al₂O₃−682 2846 B₂O₃ + 2B + C + 2Al B₄C + Al₂O₃ −464 2200 Mo + 2Se MoSe₂ −1542213 Fe₂O₃ + 2Al A1₂O₃ + 2Fe −853 2862 3CaO + P₂O₃ Ca₃(PO₄)₂ −170 2083

TABLE II Examples with Diluent/Intermediary Reactant/Catalyst/SolventSpecies: For Energy T_(ad(298K)) Reactants Products x, y (kJ) (K) Ti +C + xTiC (1 + x)TiC 1 −185 2075 5 −185 964 Ti + C + xTiC + (1 + x)TiC +yAl 1, 1 −185 1634 yA1 2, 5 −185 933 Ti + C + xNi TiC + xNi 1 −185 21935 −185 1193 Ti + 2B + xNi TiB₂ + xNi 1 −280 2498 5 −280 1488 3Ti + B₄C +xAl 2TiB₂ + TiC + xAl 1 −682 2096 10 −682 1462 W + C + xCo WC + Co 1 −40840 0.33 −40 1018 Fe₂O₃ + 2Al + xFe Al₂O₃ + (2 + x) + Fe 1 −853 2927 15−853 1536 (3 + x)SiO₂ + 4Al + xSiO₂ + (3 + y)SiC + 1, 1 −906 2068 ySi +(3 + y)C 2Al₂O₃ 2, 5 −1194 1878

TABLE III Examples involving gas phase reactants: Reactants ProductsEnergy (kJ) Ti + ½ N₂ TiN −338 3Si + 2N₂ Si₃N₄ −829 2Al + 3/2 O₂ Al₂O₃−1676 Zr + H₂ ZrH₂ −169 Zr + O₂ ZrO₂ −1100 Zr + O₂ + xZrO₂ (1 + x)ZrO₂−1100 Zr + O₂ + xCaO ZrO₂ + CaO −1100

Article Examples Example 1 TiB₂—TiC—85Al

An exothermically reactive mixture containing by weight 76.8% aluminum,16.8% titanium, and 6.5% boron carbide powders was designed to produce aproduct with an aiuminum matrix and ceramic reinforcing phasescomprising by volume 85% aluminum, 10.75% titanium diboride, and 4.25%titanium carbide. The mixture has a calculated adiabatic reactiontemperature of 933 Kelvin. A mixture with a total weight of 4000 g. wasprepared by weighing the constituent powders according to thepercentages above. The powders were mixed using a motorized tumbler. Themixed powders were then placed in the dispenser tray of an EOS M290direct metal laser sintering (DMLS) machine, available from EOS of NorthAmerica, Inc. of Novi, Mich. (US).

Three dimensional models of articles for manufacture were designed usinga computer aided design (CAD) software program and digitally sliced intolayers corresponding to the thickness of one layer of powder to bespread. The digital information was sent to the EOS M290 DMLS machine.

The processing chamber of the M290 DMLS machine was flooded with argongas and a layer of the powder mixture having a thickness of about 30 μmwas spread across an aluminum base plate by a re-coater blade. The M290ytterbium fiber laser traced the first slice of the articles onto thepowder layer, thereby heating the traced regions to a temperatureadequate to initiate the exothermic chemical reaction. The combinedenergy from the laser and chemical reaction in the traced regions wasadequate to initiate the exothermic chemical reaction. The combinedenergy from the laser and chemical reaction in the traced regions wasadequate to produce fusion by sintering and melting of the productmaterials to themselves and to the aluminum alloy build plate. A secondlayer of the powder mixture was then spread over the first layer by there-coater blade and the second slice of the articles was traced by thelaser to initiate the chemical reaction in this layer. The energy of thelaser and chemical reaction caused the traced regions of the secondlayer to fuse to itself and to the first layer. The process was thenrepeated layer-by-layer until the complete article had beenmanufactured. The finished articles were then removed from the buildplate by cutting them off with a band saw.

A total of 20 articles were manufactured on the build plate in oneproduction run using either single or double laser exposures per layerwith unique combinations of laser power and travel velocity settings foreach part. The product phases of the articles were examined by x-raydiffraction and scanning electron microscopy (SEM) and found to beprimarily titanium diboride and titanium carbide in an aluminum matrix.An SEM micrograph of one of the Example 1 articles is reproduced hereinas FIG. 4.

The densities of the parts were measured relative to the theoreticaldensity of 3.00 g/cm³ using Archimedes method and found to havetheoretical densities in a range of from about 92.04% to about 99.63%,depending on the combination of laser exposures and laser power andtravel velocity used for the part. Hardness values were measured usingthe Rockwell B scale (HRB) with measurements found to average 62.9 HRB(approximately 1100 MPa) for a part with a high relative density. Themeasured hardness of the aluminum matrix composites compares favorablyto literature values for commercially pure aluminum with a reportedBrinell hardness of 30 BHN500 (approximately 294 MPa) which is belowzero on the HRB scale.

Example 2 (Ti—V)B₂, C-85Al—Mg Matrix

An exothermically reactive mixture containing by weight 75.19%aluminum/4.5% magnesium alloy powder, 18.23% titanium/6% aluminum/4%vanadium powder, and 6.58% boron carbide powder was designed to producea product with an aluminum/4.5% magnesium matrix comprising by volume85% and ceramic reinforcing phases comprising by volume 15% titanium andvanadium diborides and carbides. The mixture has a calculated adiabaticreaction temperature of 933 Kelvin. A mixture with a total weight of4000 g. was prepared by weighing the constituent powders according tothe percentages above. The powders were mixed using a motorized tumbler.The mixed powders were then placed in the dispenser tray of the EOS M290direct metal laser sintering (DMLS) machine.

Three dimensional models of articles for manufacture were designed usinga computer aided design (CAD) software program and digitally sliced intolayers corresponding to the thickness of one layer of powder to bespread. The digital information was sent to the EOS M290 DMLS machine.

The processing chamber of the DMLS machine was flooded with argon gasand a layer of the powder mixture having a thickness of about 30 μm wasspread across an aluminum build plate by a re-coater blade. The M290ytterbium fiber laser traced the first slice of the articles onto thepowder layer, thereby heating the traced regions to a temperatureadequate to initiate the exothermic chemical reaction. The combinedenergy from the laser and chemical reaction in the traced regions wasadequate to produce fusion by sintering and melting of the productmaterials to themselves and to the aluminum alloy build plate. A secondlayer of the powder mixture was then spread over the first layer by there-coater blade and the second slice of the articles was traced by thelaser to initiate the chemical reaction in this layer. The energy of thelaser and chemical reaction caused the traced regions of the secondlayer to fuse to itself and to the first layer. The process was thenrepeated layer-by-layer until the complete articles had beenmanufactured. The finished articles were then removed from the buildplate by wire electrical discharge machining (EDM).

A total of 20 articles were manufactured on the build plate in oneproduction run using either single or double laser exposures per layerwith unique combinations of laser power and travel velocity settings foreach part. The product phases of the articles were examined by x-raydiffraction and SEM and found to be primarily titanium diboride andtitanium carbide with lesser amounts of vanadium diboride and carbide inan aluminum-magnesium alloy matrix. The densities of the parts weremeasured relative to the theoretical density of 2.95 g/cml usingArchimedes method and found to range from about 97.7% to about 100%theoretical, depending on the combination of laser exposures and laserpower and travel velocity used for the part. Hardness values weremeasured using the Rockwell B scale (HRB) and found to average 90.4 HRB(approximately 1900 MPa) for a part with 100% relative density. Themeasured hardness of the aluminum matrix composites compares favorablyto literature values for commercially pure aluminum with a hardness of30 BHN500 (approximately 294 MPa) which is below zero on the HRB scale.The hardness value also compares favorably with that of the purealuminum matrix composite described in Example 1.

Example 3 NiTi

An exothermically reactive mixture containing by weight 55.5% nickel and44.5% titanium was designed to produce a product comprised ofintermetallic nickel-titanium shape memory alloy. The mixture has acalculated adiabatic reaction temperature of 1438 Kelvin. A mixture witha total weight of 2500 g. was prepared by weighing the constituentpowders according to the percentages above. The powders were mixed usinga motorized tumbler. The mixed powders were then placed in the dispensertray of the EOS M290 direct metal laser sintering (DHLS) machine.

Three dimensional models of articles for manufacture were designed usinga computer aided design (CAD) software program and digitally sliced intolayers corresponding to the thickness of one layer of powder that willbe spread. The digital information was sent to the EOS M290 DMLSmachine.

The processing chamber of the DMLS machine was flooded with argon gasand a layer of the powder mixture having a thickness of about 40 μm wasspread across a 316L stainless steel build plate by a re-coater blade.The M290 ytterbium fiber laser traced the first slice of the articlesonto the powder layer, thereby heating the traced regions to atemperature adequate to initiate the exothermic chemical reaction. Thecombined energy from the laser and chemical reaction in the tracedregions was adequate to produce fusion by sintering and melting of theproduct materials to themselves and to the 316L alloy build plate. Asecond layer of the powder mixture was then spread over the first layerby the re-coater blade and the second slice of the articles was tracedby the laser to initiate the chemical reaction in this layer. The energyof the laser and chemical reaction caused the traced regions of thesecond layer to fuse to itself and to the first layer. The process wasthen repeated layer-by-layer until the complete articles had beenmanufactured. The finished articles were then removed from the buildplate by cutting them off with a band saw.

A total of 12 articles were manufactured on the build plate in oneproduction run using either single or double laser exposures per layerwith unique combinations of laser power and travel velocity settings foreach part. The product phases of the articles were examined by x-raydiffraction and SEM and found to be primarily one-to-one nickel-titariumintermetallic. The densities of the parts were measured relative to thetheoretical density of 6.5 g/cm³ using Archimedes method and found torange from about 86.7% to about 97.2% depending on the combination oflaser exposures and laser power and travel velocity used for the part.The parts were suitable for shape setting with subsequent heat treatmentand mechanical deformation.

Example 4 Extrusion

An exothermicaliy reactive mixture containing by weight 55.12% titanium,13.83% carbon, and 31.06% aluminum was designed to produce a productwith an aluminum matrix comprising by volume 45% and titanium carbideparticles comprising by volume 55%. The mixture has a calculatedadiabatic reaction temperature of 2368 Kelvin. A mixture with a totalweight of 200 g. was prepared by weighing the constituent powdersaccording to the percentages above. The powders were hand shaken in aNalgene style bottle and poured into a glass beaker where 80 g. ofpropylene glycol was subsequently added. The powders were mixed with theliquid propylene glycol by hand stirring using a stainless steelstirring utensil. The mixed powders and propylene glycol slurry werethen placed in a flexible polymer bag with a nozzle attachment suitablefor extrusion of the material by application of pressure on the bagcontaining the material.

Three steel sheet metal build plates were placed onto the surface of anelectric hot plate to maintain a temperature of about 210° C. Individualarticles were extruded to each of the three sheet metal build plateswith the propylene glycol vaporizing during the extrusion process due tothe elevated temperature of the build plate. The first article extrusionwas completed by extruding the material in a continuous fashion toproduce a green part comprised of 15 continuously fed interconnectedlayers of extruded material. The second article was produced bycontinuously extruding one layer of the article and then disconnectingthe extruded material before starting the next layer. The third greenarticle was completed by extruding a series of segments on each layerwith discontinuities between the end of one segment and the start of thenext as well as discontinuities between each layer. Although theextrusion process was performed manually in this example, the process issuitable for computer based automation.

The green articles were then reacted by local contact with anoxygen-acetylene flame to locally initiate the exothermic chemicalreaction which then self-propagated throughout the article. The hightemperature chemical reaction rapidly transformed the reactant materialsinto the product phases thereby fusing and strengthening the articles aswell as vaporizing any volatile impurities such as residual propyleneglycol. The reacted articles maintained the form produced duringextrusion and exhibited have high abrasion resistance due to thehardness of the titanium carbide product phase.

Example 5 SiC

An exothermically reactive mixture containing by weight 70.0% siliconand 30.0% carbon was designed to produce a product comprised of siliconcarbide. The mixture has a calculated adiabatic reaction temperature of1852 Kelvin. A mixture with a total weight of 10 g. was prepared byweighing the constituent powders according to the percentages above. Thepowders were mixed by shaking followed by hand milling with a mortar andpestle.

An Epilog Zing laser engraver with a 40 Watt carbon dioxide laser wasmodified to include a steel die having a cylindrical bore of about 25.4mm (about 1 inch) with the die height positioned by the adjustableheight positioning table while the cylindrical press rod passed througha hole in the positioning table to sit flat on the machine base at afixed height. The Epilog Zing laser engraver was placed inside acontrolled atmosphere glove box and the glove box was flooded with argongas. The positioning table height was adjusted so that there was a gapof about 2 mm between the press rod and the top of the die. A layer ofthe mixed powders was placed on top of the press rod in the die and thelayer of powders was scraped flat by hand using a steel scraping bladeso the top of the layer was level with the top of the die.

A two-dimensional rectangular article having dimensions of about 12.7 mmby about 9.5 mm (about 0.5 inch by 0.375 inch) was designed using a CADsoftware program. The digital information was sent to the Epilog Zing 40Watt laser engraver and the laser traced the rectangular pattern ontothe powder layer, thereby heating the traced region to a temperatureadequate to initiate the exothermic chemical reaction. The combinedenergy from the laser and chemical reaction in the traced region wasadequate to produce fusion by sintering and melting of the productmaterials. The positioning table height was then raised one stepcorresponding to approximately 200 μm while the press rod positionremained stationary. A second layer of the powder mixture was thenspread over the first layer by hand and scraped level with the die topusing a steel scraping blade. The rectangular article was again tracedby the laser to initiate the chemical reaction in this layer. The energyof the laser and chemical reaction caused the traced regions of thesecond layer to fuse to itself and to the first layer. The process wasthen repeated layer-by-layer until the complete article with a thicknessor height of about 1 mm had been manufactured. The finished article wasthen removed from the surrounding unreacted powder using forceps.

The product phases of the article were examined by x-ray diffraction andfound to be primarily silicon carbide however silicon and carbon peakswere also present. The presence of the residual silicon and carbon isbelieved to be due to the layer thickness of about 200 μm being toogreat for the laser processing conditions.

Example 6 WC—Co

An exothermically reactive mixture containing by weight 75.1% tungsten,4.9% carbon, and 20.0% cobalt was designed to produce a productcomprised by weight of 80% tungsten carbide and a 20% matrix of cobalt.The mixture has a calculated adiabatic reaction temperature of 876Kelvin. A mixture with a total weight of 10 g. was prepared by weighingthe constituent powders according to the percentages above. The powderswere mixed by shaking followed by hand milling with a mortar and pestle.

An Epilog Zing laser engraver with a 40 Watt carbon dioxide laser wasmodified to include a steel die having a cylindrical bore of about 25.4mm (about 1 inch) with the die height positioned by the adjustableheight positioning table while the cylindrical press rod passed througha hole in the positioning table to sit flat on the machine base at afixed height. The Epilog Zing laser engraver was placed inside acontrolled atmosphere glove box and the glove box was flooded with argongas. The positioning table height was adjusted so that there was a gapof about 2 mm between the press rod and the top of the die. A layer ofthe mixed powders was placed on top of the press rod in the die and thelayer of powders was compacted by hand and then scraped fiat using asteel plate so the top of the layer was level with the die top.

A two-dimensional square article having dimensions of about 12.7 mm(about 0.5 inch) square was designed using a CAD software program. Thedigital information was sent to the Epilog Zing 40 Watt laser engraverand the laser traced the square pattern onto the powder layer, therebyheating the traced region to a temperature adequate to initiate theexothermic chemical reaction. The combined energy from the laser andchemical reaction in the traced region was adequate to produce fusion bysintering and melting of the product materials. The positioning tableheight was then raised one step corresponding to about 200 μm while thepress rod position remained stationary. A second layer of the powdermixture was then spread and compacted over the first layer by hand andscraped level with the die top using a steel scraping blade. The squarearticle was again traced by the laser to initiate the chemical reactionin this layer. The energy of the laser and chemical reaction caused thetraced regions of the second layer to fuse to itself, and to the firstlayer. The process was then repeated layer-by-layer until the completearticle with a height or thickness of about 1 mm had been manufactured.The finished article was then removed from the surrounding unreactedpowder using forceps.

The product phases of the articles were examined by x-ray diffractionand found to be primarily tungsten carbide and cobalt, however tungstenand carbon peaks were also present. The presence of the residualtungsten and carbon is believed to be due to the layer thickness ofabout 200 μm being too great for the laser processing conditions.

Example 7 TiB₂—TiC-Glass Matrix

An exothermicaliy reactive mixture containing by weight 50.0% glasspowder (approximately 74.5% silica, 13.5% soda, 10.5% lime, 1.5%alumina), 36.1% titanium, and 13.9% boron carbide was designed toproduce a product comprised of titanium diboride and titanium carbide ina matrix of 50 percent by weight glass. A mixture with a total weight of5 grams was prepared by weighing the constituent powders according tothe percentages above. The powders were mixed by shaking followed byhand milling with a mortar and pestle.

An Epilog Zing laser engraver with a 40 Watt carbon dioxide laser wasmodified to include a steel die having a cylindrical bore of about 25.4mm (about 1 inch) with the die height positioned by the adjustableheight positioning table while the cylindrical press rod passed througha hole in the positioning table to sit flat, on the machine base at afixed height. The Epilog Zing laser engraver was placed inside acontrolled atmosphere glove box and the glove box was flooded with argongas. The positioning table height was adjusted so that there was a gapof about 2 mm between the press rod and the top of the die. A layer ofthe mixed powders was placed on top of the press rod in the die and thelayer of powders was compacted by hand and then scraped flat using asteel plate so the top of the layer was level with the die top.

A two-dimensional rectangular article having dimensions of about 12.7 mmby about 9.5 mm (about 0.5 inch by 0.375 inch) was designed using a CADcomputer software program. The digital information was sent to theEpilog Zing 40 Watt laser engraver and the laser traced the rectangularpattern onto the powder layer, thereby heating the traced region to atemperature adequate to initiate the exothermic chemical reaction. Thecombined energy from the laser and chemical reaction in the tracedregion was adequate to produce fusion by sintering and melting of theproduct materials. The positioning table height was then raised twosteps corresponding to approximately 200 μm while the press rod positionremained stationary. A second layer of the powder mixture was thenspread and compacted over the first layer by hand and scraped level withthe die top using a steel scraping blade. The rectangular article wasagain traced by the laser to initiate the chemical reaction in thislayer. The energy of the laser and chemical reaction caused the tracedregions of the second layer to fuse to itself and to the first layer.The process was then repeated layer-by-layer until the complete articlewith a height or thickness of about 0.8 mm had been manufactured. Thefinished article was then removed from the surrounding unreacted powderusing forceps.

The product phases of the articles were examined by x-ray diffractionand found to contain primarily titanium diboride, titanium carbide, andamorphous material along with lesser amounts of reactant andintermediary phases. The presence of these additional phases is believedto be due to the layer thickness of 200 microns being too great for thelaser processing conditions.

Example 8 B₄C

An exothermically reactive mixture containing by weight 78.3% boron and21.7% carbon was designed to produce a product comprised of boroncarbide. The mixture has a calculated adiabatic reaction temperature of957 Kelvin. A mixture with a total, weight of 10 g. was prepared byweighing the constituent powders according to the percentages above. Thepowders were mixed by shaking followed by hand milling with a mortar andpestle.

An Epilog Zing laser engraver with a 40 Watt carbon dioxide laser wasmodified to include a steel die having a cylindrical bore of about 25.4mm (about 1 inch) with the die height positioned by the adjustableheight positioning table while the cylindrical press rod passed througha hole in the positioning table to sit flat on the machine base at afixed height. The Epilog Zing laser engraver was placed inside acontrolled atmosphere glove box and the glove box was flooded with argongas. The positioning table height was adjusted so that there was a gapof about 2 mm between the press rod and the top of the die. A layer ofthe mixed powders was placed on top of the press rod in the die and thelayer of powders was compacted by hand and then scraped flat using asteel plate so the top of the layer was level with the die top.

A two-dimensional rectangular article having dimensions of about 12.7 mmby about 9.5 mm (about 0.5 inch by 0.375 inch) was designed using a CADsoftware program. The digital information was sent to the Epilog Zing 40Watt laser engraver and the laser traced the rectangular pattern ontothe powder layer, thereby heating the traced region to a temperatureadequate to initiate the exothermic chemical reaction. The combinedenergy from the laser and chemical reaction in the traced region wasadequate to produce fusion by sintering and melting of the productmaterials. The positioning table height was then raised two stepscorresponding to approximately 400 μm while the press rod positionremained stationary. A second layer of the powder mixture was thenspread and compacted over the first layer by hand and scraped level withthe die top using a steel scraping blade. The rectangular article wasagain traced by the laser to initiate the chemical reaction in thislayer. The energy of the laser and chemical reaction caused the tracedregions of the second layer to fuse to itself and to the first layer.The process was then repeated layer-by-layer until the complete articlewith a height or thickness of about 5.6 millimeters had beenmanufactured. The finished article was then removed from the surroundingunreacted powder using forceps.

The product phases of the articles were examined by x-ray diffractionand found to contain boron carbide with boron and carbon peaks alsopresent. The presence of the residual boron and carbon is believed to bedue to the layer thickness of about 400 μm being too great for the laserprocessing conditions.

Example 9 B₄C—TiB₂—SiC Eutectic

An exothermically reactive mixture containing by weight 61.3% boron,25.1% carbon, 11.1% silicon, and 2.5% titanium was designed to produce aternary eutectic ceramic product comprised of boron carbide, siliconcarbide, and titanium diboride. The mixture has a calculated adiabaticreaction temperature of 1403 Kelvin. A mixture with a total weight of 10g. was prepared by weighing the constituent powders according to thepercentages above. The powders were mixed by shaking followed by handmilling with a mortar and pestle.

An Epilog Zing laser engraver with a 40 Watt carbon dioxide laser wasmodified to include a steel die having a cylindrical bore of about 25.4mm (about 1 inch) with the die height positioned by the adjustableheight positioning table -while the cylindrical press rod passed througha hole in the positioning table to sit flat on the machine base at afixed height. The Epilog Zing laser engraver was placed inside acontrolled atmosphere glove box and the glove box was flooded with argongas. The positioning table height was adjusted so that there was a gapof about 2 mm between the press rod and the top of the die. A layer ofthe mixed powders was placed on top of the press rod in the die and thelayer of powders was scraped flat by hand using a steel scraping bladeso the top of the layer was level with the die top.

A two-dimensional rectangular article having dimensions of about 12.7 mmby about 9.5 mm (about 0.5 inch by 0.375 inch) was designed using a CADsoftware program. The digital information was sent to the Epilog Zing 40Watt laser engraver and the laser traced the rectangular pattern ontothe powder layer, thereby heating the traced region to a temperatureadequate to initiate the exothermic chemical reaction. The combinedenergy from the laser and chemical reaction in the traced region wasadequate to produce fusion by sintering and melting of the productmaterials. The positioning table height was then raised one stepcorresponding to approximately 200 μm while the press rod positionremained stationary. A second layer of the powder mixture was thenspread over the first layer by hand and scraped level with the die topusing a steel scraping blade. The rectangular article was again tracedby the laser to initiate the chemical reaction in this layer. The energyof the laser and chemical reaction caused the traced regions of thesecond layer to fuse to itself and to the first layer. The process wasthen repeated layer-by-layer until the complete article with a height orthickness of about 1.4 mm had been manufactured. The finished articlewas then removed from the surrounding unreacted powder using forceps.

Example 10 TiC—TiC Diluent

An exothermically reactive mixture containing by weight 40.0% titanium,10.0% carbon, and 50.0% titanium carbide diluent was designed to producea product comprised of titanium carbide. The diluent titanium carbidewas added to lower the reaction temperature to prevent propagation ofthe reaction outside of the regions intended to comprise the designedarticles. The mixture has a calculated adiabatic reaction temperature of2076 Kelvin. A mixture with a total weight of 10 g. was prepared byweighing the constituent powders according to the percentages above. Thepowders were mixed by shaking followed by hand milling with a mortar andpestle.

An Epilog Zing laser engraver with a 40 Watt carbon dioxide laser wasmodified to house a removable steel die having a cylindrical bore with adiameter of about 25.4 mm (about 1 inch). A layer of the mixed powderswas pressed in the die at 1 metric ton-force between two press rods andthe upper press rod was pressed out with the compacted powder remainingin the die. The die and compacted powder were placed in the laserengraver and the processing chamber was flooded with argon gas.

A two-dimensional rectangular article having dimensions of about 12.7 mmby about 9.5 mm (about 0.5 inch by 0.375 inch) was designed using a CADsoftware program. The digital information was sent to the Epilog Zing 40Watt laser engraver and the laser traced the rectangular pattern ontothe powder layer, thereby heating the traced region to a temperatureadequate to initiate the exothermic chemical reaction. The combinedenergy from the laser and chemical reaction in the traced region wasadequate to produce fusion by sintering and melting of the productmaterials. Additional mixed powder totaling 0.1 g. was added on top ofthe first layer and again compacted using one metric ton-force and thedie and compacted powder was placed in the laser engraver. Theprocessing chamber was again flooded with argon gas and the rectangulararticle was again traced by the laser to initiate the chemical reactionin this layer. The energy of the laser and chemical reaction caused thetraced regions of the second layer to fuse to itself and to the firstlayer. The finished article was then removed from the surroundingunreacted powder using forceps.

The product phases of the articles were examined by x-ray diffractionand found to contain primarily titanium carbide with lesser amounts oftitanium and carbon also present. The presence of the residual boron andcarbon is believed to be due to incomplete removal of surroundingpowders and due to the layer height being too high for the laserprocessing conditions.

Example 11 Ti—TiN

A powder containing by weight 100% titanium was designed toexothermically react with nitrogen gas in an atmosphere comprised of 90%argon and 10% nitrogen gases at a pressure of one atmosphere to producea product comprised of titanium nitride and titanium metal.

An Epilog Zing laser engraver with a 40 Watt carbon dioxide laser wasmodified to include a steel die having a cylindrical bore of about 25.4mm (about 1 inch) with the die height positioned by the adjustableheight positioning table while the cylindrical press rod passed througha hole in the positioning table to sit flat on the machine base at afixed height. The Epilog Zing laser engraver was placed inside acontrolled atmosphere glove box and the glove box was flooded with themixture of argon and nitrogen gases. The positioning table height wasadjusted so that there was a gap of about 2 mm between the press rod andthe top of the die. A layer of the mixed powders was placed on top ofthe press rod in the die and the layer of powders was scraped flat byhand using a steel scraping blade so the top of the layer was level withthe die top.

A two-dimensional rectangular article having dimensions of about 12.7 mmby about 9.5 mm (about 0.5 inch by 0.375 inch) was designed using a CADsoftware program. The digital information was sent to the Epilog Zing 40Watt laser engraver and the laser traced the rectangular pattern ontothe powder layer, thereby heating the traced region to a temperatureadequate to initiate the exothermic chemical reaction with the nitrogengas. The rate and extent of the reaction was kinetically limited by theavailability of nitrogen. The combined energy from the laser andchemical reaction in the traced region was adequate to produce fusion bysintering and melting of the product materials. The positioning tableheight was then raised one step corresponding to approximately 200 μmwhile the press rod position remained stationary. A second layer of thepowder mixture was then spread over the first layer by hand and scrapedlevel with the die top using a steel scraping blade. The rectangulararticle was again traced by the laser to initiate the chemical reactionin this layer. The energy of the laser and chemical reaction caused thetraced regions of the second layer to fuse to itself and to the firstlayer. The process was then repeated layer-by-layer until the completearticle with a height or thickness of about 1 mm had been manufactured.The finished article was then removed from the surrounding unreactedpowder using forceps.

The product was found to have a gold color characteristic of titaniumnitride and also contain unreacted titanium metal. The amount of productphase converted to titanium nitride can be increased by increasing thenitrogen concentration and pressure as well as by decreasing thetitanium particle size and layer thickness.

Having herein set forth preferred embodiments of the present invention,it is anticipated that suitable modifications can be made thereto whichwill nonetheless remain within the scope of the invention. The inventionshall therefore only be construed in accordance with the followingclaims:

1. An additive manufacturing method of producing an article, comprising:a) providing a blended powder comprising a first powder material and asecond powder material, the first and second powder materials capable ofchemically reacting with one another upon the addition of energy to forma reaction product, said first powder material being provided in excessof a stoichiometric amount; b) forming the blended powder into a firstlayer; c) subjecting at least a portion of the first layer to energysufficient to initiate the chemical reaction between the first andsecond materials to form the reaction product, unreacted amounts of thefirst material absorbing heat produced by the chemical reaction betweenthe first and second materials, the reaction product and unreactedamounts of the first material in the first layer forming at least aportion of the article; d) providing additional quantities of theblended powder over the first layer to form a second layer; and e)subjecting at least a portion of the second layer to energy sufficientto initiate the chemical reaction between the first and second powdermaterials to form the reaction product, the reaction product andunreacted amounts of the first material in the second layer also forminga portion of the article.
 2. The method of claim 1, further comprisingrepeating steps d) and e) until the article is formed in its entirety.3. The method of claim 1, wherein said subjecting at least a portion ofthe first layer to energy comprises subjecting at least a portion of thefirst layer to directed energy sufficient to initiate the chemicalreaction between the first and second materials, and wherein saidsubjecting at least a portion of the second layer to energy comprisessubjecting at least a portion of the second layer to directed energysufficient to initiate the chemical reaction between the first andsecond materials.
 4. The method of claim 1, wherein said subjecting atleast a portion of the first layer to energy comprises subjecting atleast a portion of the first layer to localized energy sufficient toinitiate the chemical reaction between the first and second materials,and wherein said subjecting at least a portion of the second layer toenergy comprises subjecting at least a portion of the second layer tolocalized energy sufficient to initiate the chemical reaction betweenthe first and second materials.
 5. The method of claim 3, wherein saidsubjecting the first and second layers to directed energy comprisesdirecting a laser beam on the first and second layers.
 6. The method ofclaim 3, wherein said subjecting the first and second layers to directedenergy comprises directing an electron beam on the first and secondlayers.
 7. The method of claim 6, wherein said subjecting the first andsecond layers to directed energy comprises subjecting the first andsecond layers to an electric plasma arc.
 8. The method of claim 1,wherein said forming and subjecting steps are conducted in an inertatmosphere.
 9. The method of claim 1, further comprising: providing asupply of a process gas, the process gas capable of chemically reactingwith at least one of the first and second materials; and wherein saidforming and subjecting steps are conducted in an atmosphere comprisingthe process gas so that the process gas chemically reacts with at leastone of the first and second materials.
 10. The method of claim 1,wherein; said step of providing a blended powder comprises providing ablended powder comprising a first powder material, a second powdermaterial, and a third powder material, at least one of the first,second, and third powder materials capable of chemically reacting withat least one of the other of the first, second and third powdermaterials to form at least one reaction product; wherein said stepsubjecting at least a portion of the first layer comprises subjecting atleast a portion of the first layer to energy sufficient to initiate thechemical reaction between the at least one of the first, second, andthird powder materials and the at least one of the other of the first,second, and third powder materials to form the at least one reactionproduct, the at least one reaction product and unreacted amounts of thefirst material comprising at least a portion of the article; and whereinsaid step of subjecting at least a portion of the second layer comprisessubjecting at least a portion of the second layer to energy sufficientto initiate the chemical reactions between the at least one of thefirst, second, and third powder materials and the at least one of theother of the first, second, and third powder materials to form the atleast one reaction product, the at least one reaction product andunreacted amounts of the first material comprising at least a portion ofthe article.
 11. The method of claim 10, wherein the first powdermaterial comprises aluminum, wherein the second powder materialcomprises titanium powder, and the third powder material comprises boroncarbide.
 12. A method of producing an article, comprising: providing apowder comprising a first material and a metal powder, the firstmaterial and metal powder capable of chemically reacting with oneanother with the addition of energy to form a reaction product, themetal powder being provided in excess of a stoichiometric amount;forming the powder into a first layer; subjecting a portion of the firstlayer to directed energy sufficient to initiate the chemical reactionbetween the first material and the metal to form the reaction product,unreacted amounts of the metal absorbing heat produced by the chemicalreaction between the first material and the metal, the reaction productnucleating crystallization of the unreacted amounts of the metal to forma crystallized matrix, the reaction product and crystallized matrixforming a portion of the article; providing additional quantities of thepowder over the first layer to form a second layer; and subjecting atleast a portion of the second layer to directed energy sufficient toinitiate the chemical reaction between the first material and the metalto form the reaction product, unreacted amounts of the metal reducing anextent of propagation of the chemical reaction between the firstmaterial and the metal, the reaction product nucleating crystallizationof the unreacted amounts of the metal to form a crystallized matrix, thereaction product and crystallized matrix in the second layer alsoforming a portion of the article.
 13. The method of claim 12, whereinsaid step of providing a powder comprises providing a powder comprisinga first material and a metal alloy powder, the first material and metalalloy powder capable of chemically reacting with one another with theaddition of energy to form a reaction product.
 14. The method of claim12, wherein said subjecting the first and second layers to directedenergy comprises directing a laser beam on the first and second layers.15. The method of claim 14, wherein said directing a laser beam on thefirst and second layers comprises directing the laser beam having awavelength in an infrared wavelength range.
 16. The method of claim 12,wherein said subjecting the first and second layers to directed energycomprises directing an electron beam on the first and second layers. 17.The method of claim 12, wherein said subjecting the first and secondlayers to directed energy comprises subjecting the first and secondlayers to an electric plasma arc.
 18. The method of claim 12, whereinsaid forming and subjecting steps are conducted in an inert atmosphere.19. The method of claim 12, further comprising: providing a supply of aprocess gas, the process gas capable of chemically reacting with atleast one of the first material and the metal powder material; andwherein said forming and subjecting steps are conducted in an atmospherecomprising the process gas so that the process gas chemically reactswith at least one of the first material and the metal powder material.20. The method of claim 12, wherein said step of providing a powdercomprises providing a powder comprising a first material, a metalpowder, and a third material, the first, metal, and third materialscapable of chemically reacting with at least one of the other of thefirst, metal, and third materials to form at least two reactionproducts; wherein said step subjecting at least a portion of the firstlayer comprises subjecting at least a portion of the first layer toenergy sufficient to initiate the chemical reactions between the first,metal, and third materials to form the at least two reaction products,the reaction products and crystallized matrix in the first layercomprising at least a portion of the article; and wherein said step ofsubjecting at least a portion of the second layer comprises subjectingat least a portion of the second layer to energy sufficient to initiatethe chemical reactions between the first, metal, and third materials toform the at least two reaction products, the reaction products andcrystallized matrix in the second layer comprising at least a portion ofthe article.